含全氟聚醚聚氨酯丙烯酸酯的合成及性能研究

以异佛尔酮二异氰酸酯（ IPDI）、全氟聚醚醇（ Fluorolink E10H）、甲基丙烯酸羟乙酯（HEMA）以及聚乙二醇（ PEG）、聚四氢呋喃二醇（PTMG）、聚碳酸酯二醇（ PCDL）为原料合成 3种含氟聚氨酯丙烯酸酯（ FUA）,并作为低聚物添加到 UV固化涂料体系中。分别对 UV固化涂层的接触角、吸水率、耐摩擦性、形貌及表面组成等性能进行了研究。结果表明：以 PCDL为原料、低聚物用量为 2. 4%时具有良好的表面性能,水和正十六烷的接触角分别达到 114. 7°和 69. 7°,负载为 500 g、以无纺布为摩擦媒介摩擦 1 000次后水接触角为 107. 8°,涂层具有良好的耐摩擦性能。     

全氟聚醚改性UV固化丙烯酸酯涂料的合成与性能研究

以全氟聚醚醇、异佛尔酮二异氰酸酯(IPDI)、甲基丙烯酸羟乙酯(HEMA)为原料合成了含氟聚氨酯丙烯酸酯(FUA),以全氟聚醚醇和丙烯酰氯为原料合成了含氟丙烯酸酯(FM),通过红外手段表征了产物结构。将FUA与FM分别加入聚氨酯丙烯酸酯(PUA)体系和环氧丙烯酸酯(EA)体系,再配以活性稀释剂与光固化剂,制备了一系列UV固化涂料。研究了UV固化膜的凝胶含量、耐化学品性、硬度、水接触角、附着力。研究表明:通过全氟聚醚醇改性的丙烯酸酯类涂膜(FUA-PUA、FUA-EA和FM-PUA体系)具有良好的表面性能、耐化学品性,且加入了FUA的PUA涂层表面水接触角可以由98°提高到113°,体现了很好的疏水性能。     

UV固化含氟低聚物的制备及性能研究

首先由甲基丙烯酸十二氟庚酯（ DFHMA）与乙醇胺通过 Michael加成反应得到含氟醇;其次以含氟醇、马来酸酐和甲基丙烯酸缩水甘油酯（ GMA）合成活性含氟中间体;最后将之与异佛尔酮二异氰酸酯（ IPDI）、季戊四醇三丙烯酸酯（ PETA）反应得到可紫外光（ UV）固化的含氟低聚物。采用红外光谱、核磁共振对产物结构进行表征。以所得低聚物制备 UV固化涂膜,通过测试涂膜接触角、热稳定性、硬度等研究不同含氟醇添加量对涂膜性能的影响。结果表明：当含氟醇质量分数从 0增加到 10%时,涂膜水接触角从 56. 3°上升到 98. 2°,表面自由能由 52. 62 mN/m降至 22. 96 mN/m,且涂膜热稳定性提高,硬度提高。     

聚氨酯丙烯酸酯UV固化涂料的制备及性能研究

以甲苯二异氰酸酯(TDI)、聚氧化丙烯三醇和甲基丙烯酸羟乙酯(HEMA)为主要单体,1,6-己二醇二丙烯酸酯(HDDA)为活性稀释剂,二月桂酸二丁基锡(DBTDL)为催化剂,合成了UV固化涂料制备用聚氨酯丙烯酸酯(PUA)低聚物。研究结果表明:当n(TDI)∶n(聚氧化丙烯三醇)∶n(HEMA)=3.08∶1∶3时,PUA低聚物的Mr(相对分子质量)比较理想;当固化时间为4 min、w(PUA低聚物)=87%、w(光引发剂Irgacure184)=5%、w(HDDA)=4%和w(其他助剂)=3%(均相对于总物料质量而言)时,UV固化涂料的综合性能相对最好,其胶膜硬度为2H、附着力为1级、耐酸碱性大于72 h和Tg(玻璃化转变温度)为38.9℃。     

耐摩擦型全氟聚醚硅氧烷的制备与性能

以K型全氟聚醚醇、K型三羟基全氟聚醚、双端Z型全氟聚醚醇、烯丙基氯和三甲氧基硅烷为原料,氯铂酸为催化剂,通过硅氢加成制备了三类全氟聚醚硅氧烷。用FTIR、~1HNMR对K型全氟聚醚硅氧烷的结构进行了表征,并利用接触角和耐摩擦实验对全氟聚醚硅氧烷的耐摩擦性能进行了测试,考察了全氟硅氧烷链结构、含量、相对分子质量和硅氧烷水解促进剂对涂层耐摩擦性能的影响。结果表明:质量分数为0.1%的三类全氟聚醚硅氧烷涂层对水和正十六烷的接触角均分别高于113.1°和65.2°,具有良好的疏水疏油性能。双端Z型全氟聚醚硅氧烷(Mn=2 500)的耐摩擦性能最好,在负载质量为1 035 g时,经钢丝绒循环摩擦2 500次后,水接触角仍可保持100°以上。在K型全氟聚醚三硅氧烷(Mn=2 800)喷涂液中,添加质量浓度为0.5 mg/L的乙酸和质量分数为0.5%的异丙醇混合硅氧烷水解促进剂,可将涂层的耐摩擦性能从1 000次提升到1 100次。     

UV固化聚氨酯丙烯酸酯涂料的研制及其应用

以丙烯酸羟丙酯(HPA)、1,6-己二异氰酸酯(HDI)三聚体为主要原料合成低相对分子质量三官能度聚氨酯丙烯酸酯(PUA)低聚物,以该低聚物为主体树脂,添加活性稀释剂、丙烯酸共聚体系、光引发剂及其他涂料助剂制成紫外光(UV)固化聚氨酯丙烯酸酯涂料。同时对UV固化膜性能进行研究,分别讨论了主体树脂含量、活性稀释剂含量、丙烯酸体系含量及光引发剂含量对UV固化涂膜性能的影响,进而对涂料不同组分的种类及配比进行优化,确定了紫外光(UV)固化聚氨酯丙烯酸酯涂料的工艺配方,研究结果表明:该涂料的玻璃化温度(Tg)为60.9℃,涂膜具有较好的综合性能。     

UV固化聚氨酯改性环氧丙烯酸酯的制备

通过聚氨酯丙烯酸酯(PUA)预聚物中的端-NCO与双酚F型环氧丙烯酸酯(BPF-EA)低聚物中的侧-OH反应,制备了一种光活性聚氨酯改性环氧丙烯酸酯(PMEA)低聚物。将两种低聚物与活性稀释剂以及光引发剂均匀混合并进行了UV固化。研究了EA和PMEA低聚物及固化膜的性能。结果表明,制备的BPF-EA低聚物与自制的双酚A型环氧丙烯酸酯低聚物相比黏度大幅下降。EA和PMEA固化膜具有高的交联密度、良好的附着力以及优异的耐化学品性能。由于PUA预聚物的引入,聚合物链中具有一定量的柔性基团,PMEA固化膜的铅笔硬度、热稳定性和拉伸强度略有下降,断裂伸长率明显增加。固化膜的柔韧性变好。其中,以20%(质量分数)TPGDA为稀释剂配制的UV固化涂料,固化膜的综合性能最好。     

新型UV固化多官能度有机硅功能低聚物的合成及应用

以端含氢硅油、甲基乙烯基二氯硅烷和丙烯酸-β-羟乙酯为原料,经硅氢加成和醇解两步反应,制备了一种与UV固化涂料相容性好,新型多官能度、可UV固化的有机硅功能低聚物。优化了硅氢加成反应条件,产物结构经IR进行了表征。将有机硅功能低聚物应用于UV固化涂料,制得UV固化耐污涂料。研究了涂膜的光固化时间、耐试剂性以及热稳定性,并探究了有机硅低聚物含量与涂膜表面水接触角、吸水率和耐污性等之间的关系。硅氢加成反应的最佳条件:反应温度85℃,催化剂用量为0.4%,n(端基含氢硅油)∶n(甲基乙烯基二氯硅烷)=1∶2,溶剂甲苯的用量为30%。此条件下端基含氢硅油的转化率达到98%;将多官能度有机硅低聚物应用于UV固化涂料,制备有机硅耐污功能材料。涂膜固化时间为46 s,附着力达2级,硬度为3H,具有较好的力学性质。当有机硅低聚物质量分数为1.2%时,材料涂膜表面水接触角达到110°,具有优良的疏水性;涂膜耐水、耐盐及耐碱性较好,且对酱油、碳素墨水以及水性彩笔表现出良好的耐污性能。此外,固化膜在325℃内稳定存在,具有良好的热稳定性。     

UV固化丙烯海松酸聚氨酯丙烯酸酯的合成及其涂膜性能

以2,4-甲苯二异氰酸酯(TDI)、丙烯海松酸二甘醇聚酯二元醇和丙烯酸羟丙酯(HPA)为主要原料合成了UV固化涂料用丙烯海松酸聚氨酯丙烯酸酯(APAPUA)低聚物.对产物进行了红外表征,并考察了其光固化行为.测试了APAPUA固化膜的硬度、柔韧性及其他机械性能,同时考察了其热稳定性.结果表明该低聚物固化膜具有优良的力学性能及耐热性.     

含氟超支化聚氨酯丙烯酸酯低聚物的制备及其性能研究

采用全氟聚醚(PFPE)、异氟尔酮二异氰酸酯(IPDI)、甲基丙烯酸羟乙酯(HEMA)、超支化聚酯(H302)等制备了含氟超支化聚氨酯丙烯酸酯低聚物(HFUA),并通过FTIR(傅里叶红外光谱)表征了其结构。讨论了HFUA改性比例、含氟超支化聚合物用量和主体树脂种类对UV固化涂层的水/油接触角、吸水率、力学性能的影响。     

Acrylic polyester resins containing perfluoropolyethers structures: Synthesis,characterization, and photopolymerization

Poly(ε‐caprolactone‐b‐perfluoropolyether‐b‐εcaprolactone) (PCL–PFPE–PCL) block copolymers having different PCL block lengths and end‐capped with methacrylate groups were prepared and characterized. Spectroscopic analyses confirmed the expected molecular structure of the products. After UV curing, the films revealed the presence of two amorphous phases, corresponding to fluorinated and hydrogenated moieties, respectively. The material containing long PCL blocks showed also a crystalline phase. Surface properties of the UV‐cured films were evaluated: The surfaces have a very high hydrophobic character in spite of the presence of many polar OH groups present in the polymeric network and a high hysteresis in wetting. An enrichment of fluorine at the air‐side surface was shown by contact‐angle measurements, except when long PCL sequences are present. The θ_adv angles decreased by increasing the content of PCL, that is, by decreasing the content of fluorine. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 651–659, 2000     

Fluorinated segmented polyurethane anionomers for water–oil repellent surface treatments of cellulosic substrates

Three model structures of linear segmented anionomeric polyurethanes based on perfluoropolyether dimethylol‐terminated oligomers, isophorone diisocyanate, and dimethylol propionic acid were synthesized and obtained in the form of aqueous dispersions. The structures differed from each other in the chemical nature of the chain extender (diol or diamine) and in the content of carboxylic acid. Dispersions and polymer films were characterized by dynamic light scattering, dynamic mechanical analysis, differential scanning calorimetry, and contact angle measurements. Diluted aqueous dispersions were also evaluated as protective sizing agents in paper treatment, both as bulk modifiers and as surface treatments. Paper sheets characterized by high water and oil repellence were obtained. The results showed that performance is mainly related to the ionic group content of the polymer and to its molecular architecture. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1364–1372, 2005     

Low surface energy films based on partially fluorinated isocyanates: the effects of curing temperature

Self-stratification strategy can be used to prepare films in which both bulk and surface properties can be optimized. By using this approach, only a very small quantity of fluorinated species is needed to generate a surface with low surface energy. When cross-linking is involved during film formation, we are dealing with a competition behavior between the diffusion of fluorinated species and the formation of cross-linked network. In this study low surface energy polymeric films were prepared on the basis of partially fluorinated polyisocyanates, in combination with hydroxyl-end-capped three-armed solventless liquid oligoesters and modified hyperbranched polyesters. At a fluorine concentration of only 0.5 wt.%, contact angles of water and hexadecane can reach 120° and 80°, respectively. A surface energy as low as 10–15 mN/m can be obtained upon the addition of less than 1 wt.% of fluorine in the films. It was shown, from real time ATR-FTIR and contact angle measurements, that the curing temperatures demonstrated significant effects on the cross-linking rate as well as on the wettability of the films.     

Reaction and characterization of crosslinking hyperbranched poly (amine-ester) with succine anhydride

Basing on hydroxyl terminated hyperbranched poly (amine-ester)s (HPAEs), the cross-linking reactions and preparation of ester-crosslinked HPAE films were investigated using succine anhydride (SA) as crosslink reagent. It was proved that the cross-linking reaction between HPAE and SA followed a two-step mechanism. This mechanism provides an efficient route to prepare HPAE/SA cross-linked films, in which, the precursor films were prepared by casting HPAE/SA solution at a lower temperature, and then curing the films at a higher temperature. By varying SA content, the solid HPAE/SA films with different cross-linking degrees were prepared successfully. The highest tensile strength of the cross-linked film could reach 59.60 MPa. With all water contact angle smaller than 74.3°, the crosslinked films demonstrated good hydrophilic properties.     

Preparation,characterization of UV‐Curable Waterborne Polyurethane‐Acrylate and the application in metal iron surface protection

Hydroxyethyl methyl acrylate (HEMA) capped waterborne polyurethane‐acrylate (WPUA) oligomer was firstly prepared from isophorone diisocyanate (IPDI), polyether polyol (NJ‐220), dimethylolbutanoic acid (DMBA), HEMA via in‐situ and anionic self‐emulsifying method. Ultraviolet (UV) curable WPUA coating was obtained from HEMA‐capped oligomer, butyl acrylate (BA) and multifunctional acrylates (TPGDA) as reactive diluents, and Darocur 1173 as photoinitiator. The physical properties of WPUA oligomers, such as particle size, apparent viscosity, and surface tension were investigated. Some mechanical properties of UV‐WPUA films, such as contact angles, thermal properties, and solvent (water, HCl, NaOH, NaCl, and ethanol) resistance of UV‐WPUA coating films were measured. The surface morphologies were measured by scanning electron microscope and atomic force microscope. The surface free energy of the UV‐cured film was calculated from contact angle measurements using the Lewis acid–base three liquids method. The specific UV‐WPUA coating was selected to protect the iron materials that observed the effect of the protection. The results indicate that the prepared UV‐WPUA coating has excellent protective behavior to metal iron materials and may offer some contributions to protect iron cultural relics. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3142–3152, 2013     

分子结构中碳碳双键对水性UV聚氨酯分散体的影响

采用异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇(聚己二酸-1,4丁二醇酯)(PBA)为主要原料合成了环氧改性的、固体分约为50%的水性紫外光固化聚氨酯分散体(PUD)。通过预聚物中聚氨酯分子末端的—NCO基团与丙烯酸羟丙酯(HPA)和季戊四醇三丙烯酸酯(PETA)上的羟基发生反应,从而引入碳碳双键,使PUD具备紫外光固化的性能。研究了水性UV分散体的碳碳双键对水性聚氨酯的拉伸强度、硬度、粒径等性能方面的影响,同时对涂膜进行动态力学性能测试(DMA)和断面结构表征(SEM)。结果表明:双键含量增加,UV涂料的拉伸强度和硬度增大,分散体和涂料的其他性能基本不变;DMA测试表明随着双键含量的减小,软段的T_g(s)移向低温,硬段的T_g(h)移向高温,相分离趋于完全;SEM测试表明树脂的交联程度越大,抵抗断裂的程度也越大。     

Polyethylene Grafted Polyether Pentaerythritol Mono-Maleate to Improve Wettability of Liquid on Polyethylene Films

Blends of linear low density polyethylene (LLDPE) and linear low density polyethylene grafted polyether pentaerythritol mono-maleate (LLDPE-g-PPMM) were prepared by melt mixing. The surface of LLDPE/LLDPE-g-PPMM films with different contents of LLDPE-g-PPMM was characterized through contact angle and FT-IR spectroscopy. The tensile properties and light transmission properties of extruded films, as well as the performance of these films compared with commercial anti-fog films, were determined. The carbonyl polar groups on the surface of LLDPE/LLDPE-g-PPMM films increased, and the contact angles of water and glycerol decreased when the content of LLDPE-g-PPMM increased. LLDPE/LLDPE-g-PPMM films showed a noticeable reduction in water drop formation as the LLDPE-g-PPMM content was increased. The transmittancy and haze of LLDPE/LLDPE-g-PPMM films were improved when using increased contents of PPMM, which promotes better wetting of the water on the surface.     

Surface characteristics of water‐soluble cationic fluoro copolymers containing perfluoroalkyl,quaternized amino,and hydroxyl groups

Various water‐soluble cationic fluoro copolymers in quaternized form with perfluoroalkyl, amino, and hydroxyl groups were prepared by varying the contents of perfluoroalkyl ethyl acrylate (FA), 2‐(dimethylamino) ethyl methacrylate (DAMA), and 2‐hydroxyethyl methacrylate (HEMA). The solvent polymerization was carried out in acetone, with the subsequent addition of acetic acid to form a quaternized polymer. Polyurethanes films were prepared by curing aqueous solutions containing water‐soluble cationic fluoro copolymers and a blocked isocyanate at 190°C. The surface characteristics of the water‐soluble cationic fluoro copolymers and the polyurethanes were investigated on the basis of FA and DAMA contents. The contact angles for both water and methylene iodide (MI) on the cationic fluoro copolymer and the polyurethane increase steadily as FA content increases, and decrease gradually with increasing DAMA content. The contact angles on the polyurethane are slightly higher than those on the cationic fluoro copolymer. The cationic fluoro copolymer and the polyurethane with FA content of 40 wt % and DAMA content of <30 wt % show extremely low surface free energies of 13–15 dynes/cm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3702–3707, 2002     

Surface Properties for Blended Films of Poly(methylmethacrylate) and Terpolymers Composed of Methylmethacrylate, Methoxypoly(ethyleneglycol-methacrylate) and Poly(dimethylsiloxanemethacrylate)

Terpolymers composed of methylmethacrylate (MMA), poly(dimethylsiloxanemethacrylate) (PDMSMA) and methoxypoly(ethyleneglycolmethacrylate) (MPEGMA), which have blood compatibility, were blended with poly(methylmethacrylate) (PMMA) in order to improve their mechanical properties. It was expected that low surface free energy components such as the poly(dimethylsiloxane) (PDMS) and methoxy groups of terpolymer would predominate at the blend surface. The adsorptions of PDMS to the blended surfaces were confirmed via X-ray photoelectron spectroscopy (XPS). A large contact angle hysteresis was observed for the blended films via a dynamic contact angle. Advancing contact angles for blended films showed the same values as that of the silicone. The receding contact angles for those blends incorporating PDMSMA-rich terpolymer showed high values and decreased with hot water treatment, while MPEGMA-rich terpolymer blended films exhibited low values and maintained those values after hot water treatment. Adhesion tension relaxations for these blended films were also observed. These phenomena were interpreted to be caused by the reorganization of a hydrophobic segment to the polymer surface or hydrophilic segment to the water/polymer interface so as to decrease the surface or interfacial tension, respectively. Although the mechanical properties slightly decreased with blending of these terpolymers, the blended films could be applied for various practical uses.